Oxadiazolylphosphorus compounds for combatting animal and plant pests

ABSTRACT

Oxadiazolyl compounds of the formula   WHEREIN R1 represents alkyl, alkoxy or phenyl, R2 represents alkyl, R3 represents hydrogen, alkyl, alkenyl, alkinyl, phenyl, benzyl, phenoxy, alkoxy, carbamoyl, mono- and dialkyl carbamoyl, or alkoxy carbonyl, and X represents oxygen or sulphur, their manufacture and their use in pest control.

United States Patent [1 1 Bohner et al.

[451 Sept. 2, 1975 OXADIAZOLYLPHOSPHORUS COMPOUNDS FOR COMBATTING ANIMALAND PLANT PESTS [75] Inventors: Beat Bohner, Binningen; Willy Meyer,Basel, both of Switzerland [73] Assignee: Ciba-Geigy Corporation,Ardsley,

[22] Filed: Nov. 20, 1973 21 Appl. No.: 417,697

Related US. Application Data [63] Continuation-in-part of Ser. No.230,041, Feb. 28,

i972, abandoned.

2,212,797 9/ l 972 Germany Primary ExaminerDonald G Daus AssistantExaminerRaymond V. Rush Attorney, Agent, or F irmHarry Falber [5 7]ABSTRACT Oxadiazolyl compounds of the formula X R c O il/Rl (I) N ORwherein R represents alkyl, alkoxy or phenyl, R rep resents alkyl, Rrepresents hydrogen, alkyl, alkenyl, alkinyl, phenyl, benzyl, phenoxy,alkoxy, carbamoyl, mono and dialkyl carbamoyl, or alkoxy carbonyl, and Xrepresents oxygen or sulphur, their manufacture and their use in pestcontrol.

9 Claims, No Drawings wherein R represents alkyl, alkoxy or phenyl, Rrepresents alkyl, R represents hydrogen, alkyl, alkenyl, alkinyl,phenyl, benzyl, phenoxy, alkoxy, carbamoyl, monoand di-alkyl carbamoylor alkoxy carbonyl, and X represents oxygen or sulphur.

The alkyl, alkenyl, alkinyl and alkoxy chains represented by R,, R and Rcontain from 1 to 18 or 2 to 18 carbon atoms (in the case of the alkenyland alkinyl radicals), but preferably from 1 to 4 or 2 to 4 carbonatoms, and may be branched or straight-chain. Examples of such radicalsinclude: methyl, methoxy, ethyl, ethoxy, propyl, propoxy, isopropyl, n-,i-, sec. and tert. butyl, ally], crotonyl, methallyl, propargyl,n-butinyl.

Importance attaches to compounds of the formula X ll phenyl or benzyland X represents oxygen or sulphur, and particularly to the compounds ofthe formula o- 'N I ll if R (III) 1 R3 c co --P/ wherein R, represents C-C alkyl or C C alkoxy; R represents C C alkyl; and R represents C -Calkyl, benzyl or phenyl.

The compounds of formula (I) are manufactured according to the inventionby a) reacting a hydroxyoxadiazole of the formula O N l {I (IV) R C\ COH N with a phosphoric halide of the formula 1 Hal P (v) in the presenceof an acid binding agent, or (b) reacting a salt of a hydroxyoxadiazoleof the formula (IV) with a phosphoric halide of the formula (V).

In the formulae (IV), and (V), the symbols R R R and X have the meaningsgiven for the formula (I) and Hal represents fluorine, chlorine, bromineor iodine, but particularly chlorine or bromine.

As salts of hydroxydiazoles of the formula (IV) which are suitable forthe process according to the invention there may be used, for example,salts of monovalent metals, in particular the alkali metal salts.

The following bases, for example, are suitable as acid binding agents:tertiary amines, such as triethylamine, dimethyl aniline, pyridine,pyridine bases; inorganic bases, for example hydroxides and carbonatesof alkali and alkaline earth metals, preferably sodium and potassiumcarbonate.

It is advisable to carry out the reaction in inert solvents, for whichpurpose the following may be cited as suitable: aromatic hydrocarbons,such as benzene, toluene, petroleum ethers, chlorobenzene,polychlorobenzenes, bromobenzene; chlorinated alkanes containing from Ito 3 carbon atoms; ethers, such as dioxan, tetrahydrofuran; esters, suchas ethyl acetate; ketones, such as methyl ethyl ketone, diethyl ketone;nitriles, such as acetonitrile.

Some of the starting materials of the formula (IV) are known compounds.It is possible to manufacture them OC H by the process described inComp.Rend. 26 (1), 174-177 (1965), G. Baccar and F. Mathis, or by thenew synthesis routes:

ac id binding coclz agent 3 oc u M1 011 I R C/ c C--OH n c cl l l o N 20 I u l R -c-N=c=o NH on HCl R --c cou In the formulae, R, has the samemeaning as in formula I.

The active substances of the formula I are suitable for combating animaland plant pests of the most diverse kinds. Above all, however, they areactive against all development stages, such as eggs, larvae, nymphs,pupae and adults of insects and representatives of the order acarina,such as mites and ticks.

The compounds of the formula I may be used, for example, against thefollowing insects and representatives of the order acarina: insects ofthe families:

Tettigonidae, Tenebrionidae, Gryllidae, Chrysomelidae, Gryllotalpidae,Bruchidae, Blattidae, Tineidae,

Peduviidae, Noctindae, Phyrrhocoriae, Lymatriidae, Cimicidae, Pyralidae,Delphacidae, Culicidae, Aphididae, Tipulidae, Diaspididae, Stomoxydae,

Pseudococcidae, Trypetidae, Searabaeidae, Muscidae, Dermestidae,Calliphoridae, Coccinellidae, and, Pulicidae.

Acarida of the families:

lxodidae, Argasidae, Tetranychidae, and Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadenedand adapted to suit the particular circumstances by the addition ofother insecticides and/or acaricides.

Suitable additives include, for example, the following activesubstances: organic derivatives of phosphorus, formamidines, ureas,carbamic acid derivatives, and chlorinated hydrocarbons.

Moreover, the compounds of the formula I possess nematocidal propertiesand may be used, for example, to combat a wide variety of plantparasitic nematodes.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and- /or additives. Suitable carriersand additives can be solid or liquid and correspond to the substancesconventionally used in formulation technique such, for example, assolvents dispersants, wetting agents, adhesives, thickeners, bindersand/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions in the conventional formulation which iscommonly employed in application terminology, Mention may also be madeof cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby initmately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may be available and can be used in the following forms:Solid forms:

Dusts, tracking agents, granules, coated granules,

impregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water: wettable powders,pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,S10 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predeterminable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in 'alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/litreto 600 g/litre can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and subsequently comminuting theproduct.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to ethylene oxide radicals per molecule and 8to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 toethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.Wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilize theactive substance, surface-active substance and anti-foam agents and,optionally, solvents.

Wettable powder and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, as well as alkali, ammoniumand alkaline earth metal salts of lignin sulfonic acid, in addition,alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates such as salts ofsulfated hexadecanols, heptadecanols, octadecanols, and salts ofsulfated fatty alcohol glycol ethers, the sodium salt of oleolylethionate, the sodium salt of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with theadditives mentioned above that, in Wettable powder, the solid particlesize of from 0.02 to 0.04 and in pastes, of 0.03 is not exceeded. Toproduce emulsifiable concentrates and pastes, dispersing agents such asthose cited above, organic solvents and water are used. Examples ofsuitable solvents are the following: alcohols, benzene, xylene, toluene,dimethyl sulfoxide, and mineral oil fractions boiling between 120 and350C. The solvents must be practically odorless, not phytotoxic, inertto the active substances and not readily inflammable.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substance or severalactive substances of the general formula I are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes, and mineral oils alone or mixed with each other, can beused as organic solvents.

The content of active substance in the above described agents is between0.1 to in which connection it should be mentioned that in the case ofapplication from aircraft or some other suitable means of application,it is possible to use concentrations of up to 99.5% or even pure activesubstance.

The active substances of the formula I can, for example, be formulatedas follows:

Dusts The following substances are used to manufacture a 5% and a 2%dust:

5 parts of active substance 95 parts of talcum 2 parts of activesubstance 1 part of highly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The thus obtained solution is sprayed on to kaolin, and theacetone subsequently evaporated in vacuo.

Wettable powder:

The following constituents are used for the preparation of (a) a 40%,(b) and (c) a 25%, and (d) a 10% wettable powder:

40 parts of active substance, 5 parts of sodium lignin sulphonate, 1part of sodium dibutyl-naphthalene sulphonate, 54 parts of silica acid.

25 parts of active substance, 4.5 parts of calcium lignin sulphonate 1.9parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicaacid,

19.5 parts of Champagne chalk.

28.1 parts of kaolin.

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene ethanol,

1.7 parts of Champagne chalk-hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

10 parts of active substance, 7

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then groung in the appropriate mills androllers. Wettable powder are obtained which can be diluted with water togive suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to produce (a) a 10% and (b) a 25%emulsifiable concentrate:

10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

1 part of epichlorohydrin, 94 parts of benzene (boiling limits 160190C).

EXAMPLE 1 A. Manufacture of 0.0-diethyl--[5-phenyll ,2,4-oxadiazolyl-( 3thiophosphate Manufacture of the starting material a. Within 30 minutes1 mol of benzimidoethyl ether added dropwise at 0l0C to 0.6 mols ofphosgene in 500 ml of toluene. After stirring for 1 hour at 0l0C,

nitrogen was blown through the suspension. Upon filtering off theprecipitated benzimidoethyl ether hydrochloric, the filtrate wasconcentrated, leaving as residue the not very stable acid chloride ofthe formula b. 29.9 Grams of hydroxylamine hydrochloric 64 ml ofpyridine and 600 ml of toluene were boiled for 30 minutes. After themixture had cooled to C, 76.3 g of the compound of the formula dissolvedin 200 ml of tetrahydrofuran were added dropwise at 2030C within 20minutes.

The suspension was wholly concentrated after being boiled for 3 hoursand the residue treated with 300 ml of water.

The precipitated crystals of the compound of the forhave a melting pointof 198-l99C after processing and recrystallisation from toluene.

Manufacture of Active Substance No. 1

16.2 Grams of 3-hydroxy-5-phenyl-l ,2,4-oxadiazole, 13.85 g of K CO and280 ml of acetonitrile were stirred for 2 hours at 70C. After thesuspension had cooled to C, 15.8 ml of chlorothiophosphoric diethylester in 85 ml of acetonitrile were added dropwise within 30 minutes.After being stirred for 22 hours at 5055C, the suspension was cooled to20C, filtered and completely concentrated. After chromatography oversilica gel the active substance of the formula was obtained in the formof a pale yellow liquid with a refractive index of 1.5388.

B. Manufacture of v 0,0-diethyl-()-[S-t-butyl-1,2,4-oxadiazolyl-(3)] C HS thiophosphate. I I I II Manufacture of the starting material 5 HCC\COP OCH3 l .473 A suspension of 14.4 g of hydroxylamine hydrochlo- CH NOCH ride and 28.5 g of potassium carbonate in 300 ml of tetrahydrofuranwas heated for 2 hours to reflux. 25.4 Grams of (CH;.) CO-NCO were thenadded dropwise at 30-35C within 20 minutes. The mixture was heated toreflux for 2 hours, the undissolved salts were N filtered off and thesolvent evaporated in vacuo. The CH I I 5 residue was taken up in2NaOI-l and extracted once (I: 00 H 2a with ethyl acetate. After theaqueous phase had been HC- C-O-P 2 5 l .467 acidified with 2N HCl, thecompound of the formula CH C H 011., I I l m N OH CH (I) N w I If CH 1HC- -o-P HDZLI 1.481 crystallised out. CH I CC H After recrystallisationfrom ether, the melting point 3 2 5 was 9799C.

Manufacture of Active Substance No. 2 161 Grams of K CO were added to asolution of 9 16.6 g of 3-hydroxy-5-tbutyl-l,2,4-oxadiazole in 290 I I 50c U ml of methyl ethyl ketone. After 2 hours stirring at 1/ Ch (flip! 25 70C, the mixture was cooled to 50C, 21.7 g of \Z/ 2 h \OC hchlorothiophosphoric diethyl ester in 90 ml of methyl 2 5 ketone wereadded and the batch was stirred for 20 hours at 50-55C. The undissolvedsalts were filtered 24 off and the filtrate was freed from solvent invacuo, 75

when 33.4 g of active substance of the formula CH7 O N S 40 0 N I J I II OC H CH C 0 P OC H II 3 7 were obtained in the form of a pale yellowoil with a refractiveindex of n,, 1.6687.

The following compounds were manufactured in analogous manner: O N S I HOCH ca =CH-C l-o-p 3 20 2 s n 1.5307 l C D c c 0 P 5 g N Z S 6O 0N O N lI S I 0 I I D ocn C C O I OCH3 m.p. 49 52 I 3 cu o-c C-O-P 3 N OCH N ocniii OCH 3 -OP \OCH3 OCH OCH

n ocn EXAMPLE 2 A. Insecticidal ingest poison action Tobacco and potatoplants are sprayed with a 0.05% aqueous emulsion (obtained from aemulsifiable concentrate).

After the coating has dried, Egyptian cotton leaf worms (Spodupteraliteralis) are settled on the tobacco plants and Colarado potato beetlelarvae (Leptinotarsa decemlineam) on the potato plants. The test iscarried out at 24C and 60% relative humidity.

B. Systemic insecticidal action EXAMPLE 3 Action against Chilosuppressalis Six rice plants at a time of the variety Caloro weretransplanted into plastic pots (diameter at the top 17 cm) and reared toa height of about 60 cm. Infestation with C/zilo suppressalis larvae (L3-4 mm long) took place 2 days after application of the active substancein granule form to the paddy water (rate of application: 8 kg of activesubstance per hectare). Evaluation of the insecticidal action took place10 days after application of the granules.

The compounds according to Example I were active in the above testagainst Chilo suppressalis.

EXAMPLE 4 Sterilised compost earth was homogeneously mixed with awettable powder containing 25% of active substance so that thereresulted a rate of application of 8 kg of active substance per hectare.

Young zucchetti plants (Cucumis pepo) were put into plastic pots withthe treated soil (3 plants per pot; diameter of pot 7 cm). Each pot wasinfected immediately afterwards with 5 Aulacop/wra femoralis andPachmoda or Chortiphila larvae. The control was carried out 4, 8, l6 and32 days after depositing and larvae.

At l00% kill after the first control, a fresh infestation with 5 larvaeeach was carried out in the same soil sample with 3 new zucchettiplants. If the activity was less than 80%, the remaining larvae remainedin the soil sample until the control immediately following. If an activesubstance at a rate of application of 8 kg/ha still effected a kill, afurther control with 4 and 2 kg of active substance per hectare wascarried out.

In the above test, the compounds according to Example I displayed actionagainst Aulacoplwra fermoralis, Pachmoda and Chortiphila larvae.

EXAMPLE 5 Action against ticks A. Rhicephalus bursa 5 Adults ticks or 50tick larvae were counted into a glass tube and immersed for l to 2minutes in 2 ml of an aqueous emulsion from an emulsion series eachcontaining 100, 10, l and 0.1 ppm of test substance. The tube was thensealed with a standardised cotton wool plug and placed on its head, sothat the cotton wool was able to absorb the active substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice.

The compounds according to Example 1 act in the above test againstadults and larvae of Rhicephalus bursa.

B. Boophilus micruplus (larvae)- Tests are carried out in each case with20 OF- sensitive larvae using an analogous dilution series as in thecase of test A. (The resistance relates to the tolerability ofdiazinone).

The compounds according to Example 1 act in the above test againstsensitive larvae of Boophilus microplus.

EXAMPLE 6 Acaracidal action P/raseolus vulgaris (dwarf beans) have aninfested piece of leaf from a mass culture of Terrarrrclzus urricaeplaced on them 12 hours before the test for the acaricidal action. Theoccupying mobile stages are sprayed with the emulsified testpreparations from a chromatography atomiser so that the spray broth doesnot run off. The number of living and dead larvae, adults and eggs areevaluated after 2 to 7 days under a stereoscopic microscope and theresult expressed in percentages. During the interim, the treated plantsare kept in greenhouse compartments at 25C.

The compounds according to Example I are active in the above testagainst eggs, larvae and adults of Tetranychus urticae.

EXAMPLE 7 Action against soil nematodes To test the action against soilnematodes, the active substance (in a concentration of 50 ppm) isapplied to and intimately mixed with soil infected with root gallnematodes (Meloidgyne Avenaria). Immediately afterwards, tomato cuttingsare planted in the thus prepared soil in a series of tests and after awaiting time of 8 days tomato seeds are sown in another test series.

In order to assess the nematocidal action, the galls present on theroots are counted 28 days after planting and sowing respectively. Thecompounds according to Example I display a nematocidal action in theabove test.

We claim:

1. A compound of the formula wherein R represents C C alkyl or C Calkoxy, R represents C,C alkyl, R represents C,-C alkyl. benzyl, orphenyl, and X represents sulphur.

2. A compound according to claim 1 of the formula 4. A compoundaccording to claim 1 of the formula 5. A compound according to claim 1of the formula 6. A compound according to claim 1 of the formula 7. Acompound according to claim 1 of the formula 3 oc H 8. A compoundaccording to claim 1 of the formula 9. A compound according to claim 1of the formula

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 of theformula
 3. A compound according to claim 1 of the formula
 4. A compoundaccording to claim 1 of the formula
 5. A compound according to claim 1of the formula
 6. A compound according to claim 1 of the formula
 7. Acompound according to claim 1 of the formula
 8. A compound according toclaim 1 of the formula
 9. A compound according to claim 1 of the formula